EP2881381B1 - Polyglycerine partial esters, their preparation and use - Google Patents

Description

Field of the invention

The invention relates to polyglycerol partial esters of a particular composition which are capable of solubilizing very hydrophobic, oil-soluble substances in aqueous solution. The preparation and use of these polyglycol ether-free solubilizers in cosmetic formulations is also part of this invention.

State of the art

As solubilizers of oil-soluble, hydrophobic substances in water mostly non-ionic surfactants are used, which have little foam-producing effect.

By default, polyethoxylated triglycerides, especially based on castor oil, e.g. PEG-40 Hydrogenated Castor Oil, used as a solubilizer. The latter is able to approximately solubilize oil-soluble substances of very different structure and hydrophobicity in water. Also Polyglycoletherfreie Polyglycerinpartialester be used for some years as alternative solubilizers.

The disadvantage of all Polyglycerinpartialester available so far is that with their use as solubilizers for oil-soluble substances in water not so broad spectrum of substances can be covered as with the aforementioned polyethoxylated triglycerides. Thus, the polyglycerol esters are mainly suitable for the solubilization of "small" molecules, e.g. short-chain terpenes. Fatty acid based oils as well as triglycerides with long chain fatty acids, e.g. By contrast, jojoba oil, almond oil, soybean oil or avocado oil can not yet be clearly solubilized in water with the polyglycerol partial ester-based market products.

JP 2008-119568 describes the use of polyglycerol partial esters as solubilizers for oils wherein the polyglycerol partial esters are based on mixtures of saturated fatty acids having 8 to 22 carbon atoms and unsaturated fatty acids having 16 to 22 carbon atoms, wherein the molar ratio of saturated to unsaturated fatty acids are in a range of 0.2 to 0.8 to 0.8 to 0.2, based. In addition, polyglycerol partial esters of polyricinoleic acid may be added to this polyglycerol partial ester. WO 2007/027447 discloses esters of polyglycerol and hydroxyl group-containing fatty acids. The object of the present invention was to provide polyglycerol partial ester-based solubilizers which, in contrast to the products hitherto available on the market, are capable of solubilizing particularly hydrophobic, oil-soluble substances, such as long-chain triglycerides, clearly in water and in cosmetic formulations ,

Description of the invention

Surprisingly, it has been found that the Polyglycerinpartialester described below eliminate the disadvantages of the prior art and thus able to solve the task of the invention.

The invention therefore Polyglycerinpartialester which are prepared from polyglycerol by esterification with a specially selected fatty acid mixture. The products are capable of producing very hydrophobic, oil-soluble substances, e.g. long-chain triglycerides, clear in water or a cosmetic formulation to solubilize. The preparation and use of these solubilizers in cosmetic formulations is also part of this invention.

An advantage of the present invention is that the polyglycerol partial esters described herein are capable of producing highly hydrophobic, oil-soluble substances, such as e.g. long-chain triglycerides, clear in water or a cosmetic formulation to solubilize, which is not possible with the previously available polyglycerol ester-based products.

Another advantage is that the Polyglycerinpartialester described here, in contrast to polyethoxylated triglycerides can be made exclusively from renewable raw materials.

Another advantage is that the Polyglycerinpartialester described here in contrast to polyethoxylated triglycerides are liquid and therefore easy to process. Another advantage over the polyethoxylated triglycerides is that the polyglyceryl esters described herein, unlike polyethoxylated triglycerides (PEG-40 Hydrogenated Castor Oil) lead to apparently very clear dispersions of the oil in the water and no clouding occurs during storage.

Yet another advantage of the present invention is that it can provide formulations that are polyglycol ether-free.

A further advantage of the polyglycerol partial esters described here is that they can produce a pleasant feeling on the skin in cosmetic formulations.

Another advantage of the Polyglycerinpartialester described here is that they show only very little foaming in water with stirring.

Another advantage is that the Polyglycerinpartialester described here have a very little effect on foamability and foam amount in surfactant formulations, but can improve the foam creaminess.

A further advantage is that the polyglycerol partial esters described here in surfactant formulations can lead to a reduction of the irritative effect on the skin. Another advantage of the polyglycerol partial esters described here is that they can have a stabilizing effect in emulsions.

Another advantage of the products of the invention is that they are relatively stable to oxidation and more stable in terms of color, smell and appearance.

mit

• n = 2 bis 16, bevorzugt 4 - 14, besonders bevorzugt 5 - 11
• R¹, R², R³ = unabhängig voneinander gleich oder verschieden ausgewählt aus H, R⁴ und R⁵, wobei
• R⁴ = keine Hydroxylgruppe enthaltender, gesättigter oder ungesättigter Acylrest mit 6 - 22 C-Atomen, bevorzugt mit 8 - 18 C-Atomen,
• R⁵ = mindestens eine Hydroxylgruppe enthaltender, gesättigter oder ungesättigter Acylrest mit 6 - 22 C-Atomen, bevorzugt mit 14 - 22 C-Atomen oder ein Acylrest eines Oligomers von mindestens eine Hydroxylgruppe enthaltenden, gesättigten oder ungesättigten Acylresten mit 6 - 22 C-Atomen, bevorzugt mit 14 - 22 C-Atomen, wobei der Acylrest des Oligomers bevorzugt 26 bis 66 C-Atome aufweist,
• dadurch gekennzeichnet, dass das Molverhältnis der Acylreste R⁴ zu R⁵ in einem Bereich von 95:5 bis 50:50 liegt.

The present invention provides polyglycerol partial esters of the general formula I

With

• n = 2 to 16, preferably 4 to 14, particularly preferably 5 to 11
• R ¹ , R ² , R ³ = independently of one another identically or differently selected from H, R ⁴ and R ⁵ , where
• R ⁴ = hydroxyl-containing, saturated or unsaturated acyl radical having 6 to 22 C atoms, preferably having 8 to 18 C atoms,
• R ⁵ = at least one hydroxyl-containing, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, preferably having 14 to 22 carbon atoms or an acyl radical of an oligomer of at least one hydroxyl-containing, saturated or unsaturated acyl radicals having 6 to 22 carbon atoms , preferably having 14-22 C atoms, the acyl radical of the oligomer preferably having 26 to 66 C atoms,
• characterized in that the molar ratio of the acyl radicals R ⁴ to R ^{5 is} in a range from 95: 5 to 50:50.

It will be appreciated by those skilled in the art that the polyglycerol backbone present in general formula I, because of its polymeric nature, is a random mixture of various compounds. Polyglycerol may have formed ether linkages between two primary, one secondary and two secondary positions of the glycerin monomers. For this reason, the polyglycerol backbone usually does not consist exclusively of linearly linked glycerol units, but may also contain branches and cycles. For details see eg " Original synthesis of linear, branched and cyclic oligoglycerol standards ", Cassel et al., J. Org. Chem. 2001, 875-896 ,

Corresponding structures are included in the general formula I simplified in this respect.

By the term "the molar ratio of the acyl radicals R ⁴ to R ⁵ is in a range from 95: 5 to 5:95" it is clear that radicals R ⁴ and R ⁵ are present in the polyglycerol partial ester according to the invention.

Preferred polyglycerol partial esters according to the invention are characterized in that they contain structures of the general formula 1) which each have at least one radical R ⁴ and one radical R ⁵ at the same time.

The acyl radicals R ⁴ and R ⁵ may be randomly attached to the polyglycerol backbone via both primary and secondary hydroxyl groups.

All conditions such as pressure and temperature are standard conditions (20 ° C, 1 bar) unless otherwise specified. Percentages are in mass percentages unless otherwise specified.

mit M = molare Masse; OHZ = Hydroxylzahl des freien Polyglycerins.The degree of polymerization n can be determined by determining the hydroxyl number of the polyglycerol used for the synthesis of the ester according to the invention, wherein the average degree of polymerization n is linked to the hydroxyl number of the underlying polyglycerol by the following equation: $$n=\frac{\frac{2000•M\left(\mathit{KOH}\right)}{\mathit{OHN}}-M\left(\mathit{water}\right)}{\left[\left[M\left(\mathit{glycerin}\right)-M\left(\mathit{water}\right)\right]-\frac{1000•M\left(\mathit{KOH}\right)}{\mathit{OHN}}\right]}$$

with M = molar mass; OH = hydroxyl number of the free polyglycerol.

Alternatively, the degree of polymerization n can also be determined by determining the hydroxyl number of the polyglycerol obtained after complete ester hydrolysis.

Suitable determination methods for determining the hydroxyl number are in particular those according to DGF C-V 17 a (53), Ph. Eur. 2.5.3 Method A and DIN 53240.

The acyl radicals R ⁴ and R ⁵ are preferably acyl radicals of fatty acids. R ⁴ and R ⁵ may also represent mixtures of such acyl radicals, in particular technical mixtures such as in the case of R ⁴ Kokosfettsäureschnitte.

For R ⁴ , it is particularly preferred that based on all radicals R ⁴ in the polyglycerol at least 50 mol%, preferably at least 75 mol% of the acyl radicals R ^{4 are} selected from capryloyl, caproyl and lauroyl radicals.

For R ⁵ , it is particularly preferred that it is selected from Ricinoyl- and Hydroxystearoylresten, their oligomers and mixtures thereof, particularly preferably exist based on all radicals R ⁵ in Polyglycerinpartialester at least 90 mol% of the acyl radicals R ⁵ from Ricinoylresten or a mixture of Ricinoyl and Hydroxystearoylresten, wherein it is preferred that the mixture of Ricinoyl- and Hydroxystearoylresten a molar ratio of Ricinoyl- to Hydroxystearoylresten in a range of 100 to 0.1 to 50 to 50 has.

Alternatively, preferably R ^{5 is} selected from Ricinoylresten.

Preferred polyglycerol partial esters according to the invention are characterized in that the weight ratio of the polyglyceryl residue to the sum of the acyl residues R ⁴ and R ^{5 is} 85:15 to 55:45, preferably 80:20 to 60:40, particularly preferably 75:25 to 65:35.

Polyglycerol partial esters which are preferred according to the invention are further characterized in that the molar ratio of saturated to unsaturated acyl radicals in Sum of all radicals R ⁴ and R ⁵ 99: 1-1: 99, preferably 95: 5 - 50:50, particularly preferably 90:10 - 60:40.

The polyglycerol partial esters of the present invention can be prepared by conventional esterification and transesterification processes, preferably with the process according to the invention described below.

1. A) Bereitstellen eines Polyglycerins mit einem mittleren Polymerisationsgrad n = 2 bis 16, bevorzugt 4 - 14, besonders bevorzugt 5 - 11,
2. B) Acylierung eines Teils der Hydroxygruppen des Polyglycerins mit
   mindestens einem ersten Carbonsäurederivat einer oder mehrerer ersten, gesättigten oder ungesättigten, keine Hydroxygruppe enthaltenden Carbonsäuren mit 6 - 22 C-Atomen, bevorzugt mit 8 - 18 C-Atomen und
   mindestens einem zweiten Carbonsäurederivat einer oder mehrerer zweiten, gesättigten oder ungesättigten, mindestens eine Hydroxygruppe enthaltenden Carbonsäuren mit 6 - 22 C-Atomen, bevorzugt mit 14 - 22 C-Atomen, oder eines Oligomers der zweiten Carbonsäure, wobei das Oligomer bevorzugt 26 bis 66 C-Atome aufweist,
   wobei die Carbonsäurederivate ausgewählt sind aus Carbonsäuren und Carbonsäureestern, wobei als Carbonsäureester Triglyceride erfindungsgemäß bevorzugt sind,
   wobei das molare Verhältnis der Acylreste des in Verfahrensschritt B) eingesetzten ersten Carbonsäurederivats zu denen des zweiten Carbonsäurederivats in einem Bereich von 95:5 bis 5:95, bevorzugt von 85:5 bis 15:85, besonders bevorzugt 85:15 bis 50:50 liegt.

A further subject of the present invention is a process for the preparation of polyglycerol partial esters comprising the process steps:

1. A) providing a polyglycerol having an average degree of polymerization n = 2 to 16, preferably 4-14, particularly preferably 5-11,
2. B) acylation of a part of the hydroxyl groups of the polyglycerol with
   at least one first carboxylic acid derivative of one or more first, saturated or unsaturated, non-hydroxy-containing carboxylic acids having 6-22 C atoms, preferably having 8-18 C atoms and
   at least one second carboxylic acid derivative of one or more second, saturated or unsaturated, containing at least one hydroxy group carboxylic acids having 6-22 C atoms, preferably having 14-22 C atoms, or an oligomer of the second carboxylic acid, wherein the oligomer preferably 26 to 66 C Having atoms,
   wherein the carboxylic acid derivatives are selected from carboxylic acids and carboxylic acid esters, wherein as carboxylic acid esters triglycerides are preferred according to the invention,
   wherein the molar ratio of the acyl radicals of the first carboxylic acid derivative used in process step B) to those of the second carboxylic acid derivative in a range from 95: 5 to 5:95, preferably from 85: 5 to 15:85, particularly preferably 85:15 to 50:50 lies.

The carboxylic acid derivatives preferably used in the process according to the invention are fatty acid derivatives.

In the process according to the invention, it is therefore possible to carry out in process step B)
at least one first carboxylic acid and at least one second carboxylic acid,
at least one first carboxylic acid ester and at least one second carboxylic acid,
at least one first carboxylic acid and at least one second carboxylic acid ester, at least one first carboxylic acid ester and at least one second carboxylic acid ester,
at least one first carboxylic acid and at least one first carboxylic acid ester and at least one second carboxylic acid,
at least one first carboxylic acid and at least one first carboxylic acid ester and at least one second carboxylic acid ester,
at least one first carboxylic acid and at least one second carboxylic acid and at least one second carboxylic acid ester,
at least one first carboxylic acid ester and at least one second carboxylic acid and at least one second carboxylic acid ester
or
at least one first carboxylic acid and at least one first carboxylic acid ester and at least one second carboxylic acid and at least one second carboxylic acid ester are used.

A preferred process according to the invention is characterized in that based on the acyl radicals of all first carboxylic acid derivatives at least 50 mol%, preferably at least 75 mol% of the first carboxylic acids are selected from caprylic acid, capric acid and lauric acid.

It is preferred according to the invention that in the process according to the invention, based on the acyl radicals of all second carboxylic acid derivatives, at least 90 mol% of the second carboxylic acids are selected from ricinoleic acid and hydroxystearic acid.

A process preferred according to the invention is characterized in that, based on the acyl radicals of all second carboxylic acid derivatives, at least 90 mol% of the second carboxylic acids consist of ricinoleic acid and / or hydroxystearic acid, it being preferred that the second carboxylic acids have a molar ratio of ricinoleic acid residues to hydroxystearic acid residues in a range from 100 to 0.1 to 50 to 50.

Alternatively preferably, the second carboxylic acid derivative is selected from ricinoleic acid or castor oil.

It is inventively preferred that calculated in the process according to the invention, the weight ratio of the polyglycerol to the sum of the acyl radicals used first and second carboxylic acid derivatives 85:15 to 55:45, preferably 80:20 to 60:40, particularly preferably 75:25 to 65:35.

A preferred process according to the invention is characterized in that the molar ratio of the acyl radicals from saturated to those of the unsaturated carboxylic acid derivatives used in process step B) is 99: 1 to 1:99, preferably 95: 5 to 50:50, particularly preferably 90: 10 - 60:40.

A further subject of the present invention are polyglycerol partial esters obtainable by the process according to the invention, preference being given according to the invention to those partial esters which are obtainable by processes which are preferred according to the invention.

Another object of the present invention are formulations, in particular cosmetic and pharmaceutical, wherein cosmetic are particularly preferred, which contain at least one Polyglycerinpartialester invention and / or at least one Polyglycerinpartialester obtainable by the novel process.

In particular, preferred are formulations which are substantially polyglycol ether-free and substantially free of alkoxylated compounds. The term "substantially free of alkoxylated compounds" and "substantially polyglycol ether-free" in the context of the present invention is to be understood as meaning that the formulations do not contain appreciable amounts of alkoxylated or polyglycol ether-containing compounds which exert a surface-active action. In particular, by this is meant that these compounds in amounts of less than 1 wt .-%, preferably less than 0.1 wt .-%, more preferably less than 0.01 wt .-% based on the total formulation, in particular no detectable amounts , are included.

The polyglycerol partial esters of the present invention are advantageously suitable for the preparation of care and cleaning formulations, in particular for skin and skin appendages, such as liquid soaps, shower gels, oil baths, make-up removers or shampoos, shower gels, bubble baths, liquid soaps, hair shampoos, 2-in-1 shampoos, hair rinses , Permanent wave fixatives, hair dye shampoos, hair fixatives, hair conditioners, hair dressings, hair styling preparations, Use hair lotions, mousses, hair conditioners, leave-on conditioners, hair straighteners, gloss enhancers, and hair coloring agents. Thus, such uses are also the subject of the present invention.

Another object of the present invention are thus also care and cleaning formulations, in particular for skin and skin appendages, containing Polyglycerinpartialester invention.

The term "care formulation" is understood here to mean a formulation which serves the purpose of preserving an object in its original form, the effects of external influences (eg time, light, temperature, pressure, contamination, chemical reaction with others, with the object contacting reactive compounds) such as aging, fouling, material fatigue, fading, reducing or avoiding or even enhancing desired positive properties of the article. For the last point, let's say a gloss of the considered object.

Cosmetic care and cleaning formulations according to the invention may contain, for example, at least one additional component selected from the group of
emollients,
emulsifiers,
Thickeners / viscosity regulators / stabilizers,
antioxidants
Hydrotropes (or polyols),
Solids and fillers,
pearlescent,
Deodorant and antiperspirant active ingredients,
insect repellents,
Self,
Preservatives,
conditioners,
perfumes,
dyes,
cosmetic agents,
Care additives,
superfatting agents,
Solvent.

Substances which can be used as exemplary representatives of the individual groups are known to the person skilled in the art and may, for example, be EP2273966A1 be removed. This patent application is hereby incorporated by reference and thus forms part of the disclosure.

With regard to further optional components and the amounts of these components used, reference is expressly made to those relevant to the person skilled in the art Manuals, for example K. Schrader, "Basics and Formulations of Cosmetics", 2nd edition, pages 329 to 341, Hüthig book publishing Heidelberg , referenced.

The quantities of the respective additives depend on the intended use. Typical frame formulations for the respective applications are known in the art and are included, for example, in the brochures of the manufacturers of the respective basic substances and active ingredients. These existing formulations can usually be adopted unchanged. If necessary, for adaptation and optimization, the desired modifications can be made without complications by simple experiments.

Preferred novel formulations comprise above as polyglycerol partial esters preferably exposed according to the invention or polyglycerol partial esters preferably prepared according to the invention as obtainable by the process according to the invention.

It is preferred if the formulation according to the invention additionally contains at least one oil-soluble substance and water.

In the present invention, oil-soluble substances are understood to be substances which have a LogP value (logarithm of n-ocantol-water distribution coefficient, also called log K _OW ) of at least 2.

Preferred oil-soluble substances have a LogP value of at least 5.

Particularly preferred oil-soluble substances are selected from the group comprising fatty acid-based oils, triglycerides with long-chain fatty acids, cosmetic ester oils, pure hydrocarbons such as jojoba oil, almond oil, soybean oil, avocado oil, olive oil, argan oil, rapeseed oil, sunflower oil, neem oil, caprylic / capric triglyceride, shea butter, Decyl cocoate, isopropyl palmitate, myristyl myristate and isohexadecane.

Particularly preferred formulations according to the invention contain
0.1% by weight to 40% by weight, preferably 0.3% by weight to 35% by weight, particularly preferably 0.5% by weight to 10% by weight, of polyglycerol partial esters according to the invention and / or Polyglycerol partial esters obtainable by the process according to the invention, 0.01% by weight to 40% by weight, preferably 0.1% by weight to 30% by weight, particularly preferably 0.2% by weight to 2% by weight. %, oil-soluble substance and
10 wt .-% to 98 wt .-%, preferably 20 wt .-% to 95 wt .-%, particularly preferably 45 wt .-% to 90 wt .-% water.

A further subject matter of the present invention is the use of at least one polyglycerol partial ester according to the invention and / or at least one polyglycerol partial ester obtainable by the process according to the invention for solubilizing at least one oil-soluble substance in water, wherein it is preferred according to the invention above as polyglycerol partial esters preferably exposed according to the invention or above According to the invention preferably exposed Polyglycerinpartialester available to use according to the inventive method.

In the examples given below, the present invention is described by way of example, without the invention, the scope of application of which is apparent from the entire description and the claims, to be limited to the embodiments mentioned in the examples.

Examples: Example 1 Preparation of Polyglycerol Partial Esters According to the Invention 1.1. Preparation of the polyglycerol partial ester A:

Under a nitrogen atmosphere, 225 g of polyglycerol (hydroxyl number = 935 mg KOH / g) with 39.4 g of caprylic / capric acid and 20.8 g of refined coconut fatty acid and 22.1 g of ricinoleic acid and 15.5 g of hydroxystearic acid at 240 ° C until an acid number of <0.5 mg KOH / g. The water formed in the course of the reaction was distilled off continuously. After cooling to room temperature, the reaction product was present as a cloudy liquid.

1.2. Preparation of the polyglycerol partial ester B:

Under a nitrogen atmosphere, 225 g of polyglycerol (hydroxyl number = 996 mg KOH / g) with 39.4 g of caprylic / capric acid and 20.8 g of refined coconut fatty acid and 22.1 g of ricinoleic acid and 15.5 g of hydroxystearic acid at 240 ° C until an acid number of <0.5 mg KOH / g. The water formed in the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was present as a cloudy liquid.

1.3. Preparation of the polyglycerol partial ester C:

225 g of polyglycerol (hydroxyl number = 935 mg KOH / g) with 47.3 g of caprylic / capric acid and 20.8 g of refined coconut fatty acid and 17.7 g of ricinoleic acid and 12.4 g of hydroxystearic acid were stirred at 240 ° C. under an atmosphere of nitrogen until an acid number of <0.5 mg KOH / g. The water formed in the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was present as a cloudy liquid.

1.4. Preparation of the polyglycerol partial ester D:

Under a nitrogen atmosphere, 202 g of polyglycerol (hydroxyl number = 884 mg KOH / g) with 37.7 g of caprylic / capric acid and 24.9 g of refined coconut fatty acid and 23.5 g of ricinoleic acid and 12.4 g of hydroxystearic acid at 240 ° C until an acid number of <0.5 mg KOH / g. The water formed in the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was present as a cloudy liquid.

1.5. Preparation of the polyglycerol partial ester E:

Under a nitrogen atmosphere, 225 g of polyglycerol (hydroxyl number = 935 mg KOH / g) with 39.4 g of caprylic / capric acid and 23.0 g of refined coconut oil and 41.5 g of castor oil at 240 ° C until an acid number of <0.5 mg KOH / g was reached. The water formed in the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was present as a cloudy liquid.

1.6. Preparation of the polyglycerol partial ester F:

225 g of polyglycerol (hydroxyl number = 935 mg KOH / g) with 39.4 g of caprylic / capric acid and 23.0 g of refined coconut oil and 23.0 g of castor oil and 14.2 g of castor wax were stirred at 240 ° C. under an atmosphere of nitrogen until an acid number of <0.5 mg KOH / g. The water formed in the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was present as a cloudy liquid.

1.7. Preparation of the polyglycerol partial ester G:

In a first reaction, 225 g of polyglycerol (hydroxyl number = 935 mg KOH / g) under nitrogen atmosphere with 38.0 g of caprylic acid and 60 g of castor oil at 240 ° C until an acid number of <0.5 mg KOH / g was reached. The water formed in the course of the reaction was continuously distilled off.

In a second reaction, 225 g of polyglycerol (hydroxyl number = 1060 mg KOH / g) were reacted under identical reaction conditions with 41.0 g of capric acid, 23 g of castor oil and 46.0 g of refined coconut oil.

Subsequently, the two products were combined and stirred at 90 ° C until a clear, homogeneous mixture was obtained, which was present after cooling to room temperature as a cloudy liquid.

Example 2 Preparation of Non-Inventive Polyglycerol Partial Esters 2.1. Preparation of the polyglycerol partial ester H:

Under a nitrogen atmosphere, 394 g of polyglycerol (hydroxyl number = 1061 mg KOH / g) with 51.3 g of caprylic / capric acid and 23.0 g of refined coconut fatty acid and 32.8 g of oleic acid at 240 ° C until an acid number of <0.5 mg KOH / g was reached. The water formed in the course of the reaction was continuously distilled off. After cooling to room temperature, the reaction product was present as a cloudy liquid.

Example 3: Non-inventive, commercial comparative examples 3.1. TEGOSOFT® PC 41:

Standard solubilizer, polyether-free. INCI: polyglyceryl-4 caprate. Sales product of Evonik Industries AG.

3.2. NATRAGEM® S 150 NP-LQ (CM):

Solubilizer for oils, polyether-free. INCI: Polyglyceryl-4 Laurate / Sebacate (and) Polyglyceryl-4 Caprylate / Caprate (and) Water. Sales product of Croda.

3.3. TAGAT® CH 40:

Standard solubilizer, polyether-containing. INCI: PEG-40 Hydrogenated Castor Oil. Sales product of Evonik Industries AG.

In the following, the products described above were tested in cosmetic formulations.

The formulation ingredients are named in the compositions in the form of the generally accepted INCI nomenclature using the English terms. All concentrations in the application examples are given in percent by weight.

Example 4: Improved dissolving power of the polyglycerol partial esters according to the invention in comparison with the non-inventive polyglycerol partial esters in aqueous solutions

In order to investigate the dissolving power of the polyglycerol partial esters according to the invention, these were mixed with cosmetic oils and mixed with water. As oils, avocado oil (supplier: Gustav Heess) and Caprylic / Capric Triglyceride (TEGOSOFT® CT, Evonik Industries AG) were tested. It was investigated what proportion of solubilizer is necessary to completely solve 0.5% of the respective oil in water. For this purpose, the solubilizer (different amounts) was mixed well with the oil (0.5 g) and then added slowly while stirring with water (made up to 100 g). It was stirred for one hour at 45 ° C. A "clear mixture" must not turn cloudy after cooling to 20 ° C within 1 week.

Table 1 summarizes the resulting solubilizer to oil mass ratios required to obtain clear mixtures. Table 1: Solubilizer to oil ratio required for a clear solution of the oil in water avocado oil Caprylic / Capric Triglycerides Polyglycerol partial esters A 10: 1 4: 1 Polyglycerol partial esters E 8: 1 4: 1 Polyglycerol partial ester F 9: 1 4: 1 Polyglycerol partial ester G 11: 1 5: 1 Polyglycerol partial esters H (not according to the invention) > 20: 1 9: 1 TEGOSOFT® PC 41 (not according to the invention) > 20: 1 16: 1 TAGAT® CH 40 (not according to the invention) 6: 1 6: 1

From the results in Table 1 it can be seen that the polyglycerol partial esters A, E, F and G according to the invention have significantly better solubilization properties than the polyether-free comparative examples polyglycerol partial esters H and TEGOSOFT® PC 41. Surprisingly, similar solubilizer-to-oil ratios are achieved as for the polyether-containing standard solubilizer TAGAT® CH 40 and its performance even partially exceeded.

Example 5: Improved dissolving power of the polyglycerol partial esters according to the invention in comparison to the non-inventive polyglycerol partial esters in surface-active formulations

In addition to the solution properties of the polyglycerol partial esters according to the invention for oils in water, the solvent power for oils was also investigated in surfactant formulations.

For this purpose, the respective solubilizer was mixed with 0.5 g Caprylic / Capric triglycerides (TEGOSOFT® CT, Evonik Industries AG) at 60 ° C for 5 min. Then the water was slowly added at 60 ° C with stirring and stirred for 10 min. The mixture was then cooled to 30 ° C over 30 minutes. With stirring, the mixture was then treated with the surfactants.

It was investigated what proportion of solubilizer is necessary to completely solve 0.5% of the oil in the respective surfactant system. Two surfactant systems were used: a standard lauryl ether sulfate / betaine mixture (Table 2) and a polyether-free formulation (Table 3). Table 4 summarizes the solubilizer to oil mass ratios obtained necessary to obtain clear mixtures. Table 2: Formulation Y for assessing solubilization properties in a standard surfactant system solubilizer X% TEGOSOFT® CT, Evonik Industries AG, (INCI: Caprylic / Capric Triglycerides) 0.5% water ad 100.0% Texapon® NSO, BASF Cognis, 28%, (INCI: Sodium Laureth Sulfate) 32.0% TEGO® Betaine F 50, Evonik Industries AG, 38% strength, (INCI: Cocamidopropyl Betaine) 8.0% Polymer JR 400, Amerchol, (Polyquaternium-10) 0.2% Citric Acid, 30% ad pH 5.5 solubilizer X% TEGOSOFT® CT, Evonik Industries AG, (INCI: Caprylic / Capric Triglycerides) 0.5% water ad 100.0% REWOTERIC® AM C, Evonik Industries AG, 32%, (INCI: Sodium Cocoamphoacetate) 17.5% Plantacare 1200 UP, BASF Cognis, 50%, (INCI: Lauryl Glucoside) 8.8% Plantacare 818 UP, BASF Cognis, 51%, (INCI: coco-glucosides) 2.4% PERLASTAN® SC 25 Trucks, Schill & Seilacher, 25%, (Disodium / Sodium Cocoyl Glutamate) 14.4% Citric Acid, 30% ad pH 5.2 TEGOSOFT® CT in formulation Y TEGOSOFT® CT in formulation Z Polyglycerol partial esters A 6: 1 8: 1 Polyglycerol partial ester F 5: 1 6: 1 NATRAGEM® S 150 NP-LQ- (CM) (not according to the invention) 12: 1 11: 1 TEGOSOFT® PC 41 (not according to the invention) 12: 1 14: 1 TAGAT® CH 40 (not according to the invention) 8: 1 5: 1

The results in Table 4 show that polyglycerol partial esters A and F according to the invention have markedly improved solubilizer properties in comparison with the comparison products NATRAGEM® S 150 NP-LQ (CM) and TEGOSOFT® PC 41. Surprisingly, the novel Polyglycerolpartialester A and F partly also better results than with the polyether-containing product TAGAT® CH 40.

Example 6 Improved Skin Care and Foaming Properties of the Polyglycerol Partial Esters of the Invention Compared to Non-Inventive Polyglycerol Partial Esters in Surfactant Blends

To evaluate the skin care performance and the foam properties of the polyglycerol partial ester G according to the invention in aqueous, surface-active formulations, a sensory handwashing test was carried out in comparison to the comparative example TEGOSOFT® PC 41 according to the prior art.

A group of 10 trained test persons washed their hands and evaluated foam properties and skin sensation on the basis of grades ranging from 1 (poor) to 5 (very good).

The products were each tested in a standardized surfactant formulation using the standard surfactant system 9% active sodium laureth sulfate and 3% active cocamidopropyl betaine (Table 5). Tab. 5: Test formulations for the handwashing test: formulation Examples U V W Texapon® NSO-IS, BASF Cognis, 28%, (INCI: Sodium Laureth Sulfate) 32.0% 32.0% 32.0% TEGO® Betaine F 50, Evonik Industries AG, 38% strength, (INCI: Cocamidopropyl Betaine) 8.0% 8.0% 8.0% NaCl 1.5% 1.5% 1.5% citric acid 0.2% 0.2% 0.2% Water, demineralized 58.3% 55.3% 55.3% Polyglycerol partial ester G (according to the invention) - 3.0% - TEGOSOFT® PC 41 (not according to the invention) - - 3.0%

The sensory test results are summarized in Table 6. Tab. 6: Results of the handwashing test: test formulation U V W foaming behavior 3.3 3.6 3.5 foam volume 3.1 3.3 3.2 lather 2.9 4.1 3.7 Skin sensation during washing 2.9 3.1 3.0 washability 3.3 3.8 3.7 skin smoothness 2.1 2.8 2.4 Skin softness 2.3 3.1 2.8 Skin smoothness after 3 min. 3.1 3.8 3.6 Skin softness after 3 min. 2.9 3.7 3.4

From the test results in Table 6 it can be seen that the formulation V according to the invention using the polyglycerol partial ester G according to the invention is surprisingly superior in all application properties in comparison to the comparative formulation W according to the prior art. Against this background, the results of formulation V according to the invention are very good and show a clear improvement over the prior art.

On the basis of the measured values, it can be seen that the polyglycerol partial ester G according to the invention in formulation V above all leads to a significant improvement, especially in the case of foaminess, as well as skin smoothness and skin softness.

Further formulation examples:

The formulation examples given in the tables below show exemplary representatives of a large number of possible compositions according to the invention.

If the preparation of the formulation requires the separate preparation or mixture of formulation ingredients beforehand, this is referred to as a multiphase preparation. If two-phase production is required, the two phases are marked A and B in the tables given. At three- or multiphase processes, the phases with A, B and C, etc. are named. Unless otherwise indicated, the figures in the tables are by weight. In the following formulation examples, the data or wt .-% based on the respective active ingredient. However, some products are commercially available as solutions in water above all, so in these cases, depending on the active content more of the commercial products was used.

"Product Example A to G" correspond to the "polyglycerol partial esters A to G of Example 1". Tab. 7: Formulation for wet wipes Butylene glycol 2.0% glycerin 1.0% Product Example A 1.0% Silicone Quaternium-22; Polyglycerol-3 caprate; Dipropylene glycol; Cocamidopropyl betaines 0.5% allantoin 0.2% maltodextrin 0.5% Chamomilla extract 0.1% phenoxyethanol; Ethylhexyl glycerin 0.7% Perfume qs Water ad 100.0% Citric Acid, 30% ad pH 5.5 Tab. 8: cream bath Water ad 100.0% Sodium Laureth Sulfate 8.0% Coco-glucoside 4.0% Cocamidopropyl betaines 5.0% Product Example B 1.0% PEG-18 Glyceryl Oleate / Cocoate 2.0% PEG-40 Sorbitan Peroleates 1.4% Perfume 0.2% Argania Spinosa Kernel Oil 0.2% Citrus Aurantifolia (Lime) Oil 0.2% linalool 0.1% coumarin 0.1% glycerin 0.5% Glycol distearate 0.5% Styrene / acrylate copolymer 0.2% tocopherol 0.1% Preservative qs Citric Acid ad pH 5.2 Tab. 9: Cream shower Water ad 100.0% glycerin 4.0% Sodium Laureth Sulfate 4.0% Cocamidopropyl betaines 3.5% Product Example G 2.0% Coco-glucoside 2.0% Ricinus Communis Seed Oil (Seed) 0.5% Glyceryl Oleate 0.5% Argania Spinosa Kernel Oil 0.1% Butyrospermum Parkii Butter Extract 0.1% Limonene 0.1% Perfume 0.2% Acrylates / C10-30 Alkyl Acrylate Crosspolymer 0.2% Hydroxypropyl methyl cellulose 0.2% Styrene / acrylate copolymer 0.2% Sodium hydroxides 0.2% Glycol distearate 0.4% silica 0.2% tocopherol 0.1% Preservative qs Citric Acid ad pH 5.2 Tab. 10: Shower oil Helianthus Annuus Seed Oil 10.0% Ricinus Communis Seed Oil 10.0% MIPA-Laureth Sulfate 20.0% Product Example A 15.0% Laureth-4 0.5% Cocamide DEA 0.9% Perfume 0.2% Prunus Amygdalus Dulcis Oil 0.8% Argania Spinosa Kernel Oil 0.8% Water 0.5% Preservative qs Citric Acid ad pH 5.5 Tab. 11: Bath oil Water ad 100.0% Sodium Laureth Sulfate 7.0% Cocamidopropyl betaines 6.0% Cocamide DEA 2.5% Sodium Trideceth Sulfate 2.2% Product Example E 2.0% Perfume 0.5% PEG-40 Hydrogenated Castor Oil 0.1% Trideceth-9 0.2% Sodium lauroamphoacetate 0.5% Benzophenone-4 0.2% Cocamide MEA 0.4% Propylene glycol 0.5% Disodium EDTA 0.1% Sodium Chloride 0.5% glycerin 0.4% Benzyl Alcohol 0.4% Argania Spinosa Oil 0.2% Sodium Cocoyl Glutamate 0.3% phenoxyethanol 0.2% Xanthan gum 0.2% Carbomer 0.2% Lactic acid 0.3% Magnesium chlorides 0.1% coumarin 0.1% Citric Acid ad pH 5.2 Preservative qs Tab. 12: Cream shower Water ad 100.0% Sodium Laureth Sulfate 10.0% glycerin 3.0% Cocamidopropyl betaines 3.0% Product Example F 2.0% Decyl glucosides 1.5% Perfume qs Glycine Soy Oil 0.2% Helianthus Annuus Seed Oil 0.1% lecithin 0.2% Coco-glucoside 0.5% Glyceryl Oleate 0.3% coumarin 0.1% Preservative qs Tab. 13: Body shampoo Phase A Product Example F 3.0% Simmondsia chinensis (Jojoba) Seed Oil 0.7% Perfume 0.2% Phase B Sodium cocoamphoacetate 4.0% Phase C Water ad 100.0% Acrylates / C10-30 Alkyl Acrylate Crosspolymer 0.9% Phase D Sodium Lauroyl Methyl Isethionate 4.0% Caprylic / Capramidopropyl Betaine 2.0% Citric Acid 1.3% Phase E Water 10.0% Polyquaternium-7 0.3% Preservative qs Tab. 14: Body shampoo Phase A Product Example C 6.5% Simmondsia chinensis (Jojoba) Seed Oil 0.4% Perfume 0.2% Phase B Water ad 100.0% Phase C Sodium cocoamphoacetate 4.0% Phase D Water 30.0% Acrylates / beheneth-25 methacrylate copolymer 2.0% Sodium Lauroyl Methyl Isethionate 4.0% Disodium Lauryl Sulfosuccinate 2.0% Phase E Preservative qs Tab. 15: Shampoo Phase A Product Example E 3.0% Caprylic / Capric Triglycerides 0.5% Perfume 0.2% Phase B Water ad 100.0% Phase C Sodium cocoamphoacetate 7.0% Phase D glycerin 1.0% Xanthan gum 0.8% Water 25.0% Phase E Water 10.0% Acrylates / beheneth-25 methacrylate copolymer 2.0% Phase F Water 10.0% Polyquaternium-10 0.2% Phase G Cocamidopropyl betaines 5.0% Preservative qs Tab. 16: Shampoo Phase A Product Example E 8.0% Argania Spinosa Kernel Oil 0.5% Phase B Water ad 100.0% Phase C Perfume 0.3% Polyglyceryl-6-caprylates; Polyglyceryl-4 caprate; Propylene glycol 2.0% Phase D Water 20.0% Phase E Sodium Laureth Sulfate 9.0% Phase F Water 10.0% Cocamidopropyl betaines 3.0% PEG-120 methyl glucose dioleate 1.0% Phase G Water 10.0% Sodium Chloride 0.7% Polyquaternium-10 0.2% Phase H Citric Acid ad pH 5.5 Phase I Preservative qs Tab. 17: Shower gel Phase A Product Example F 3.0% Caprylic / Capric Triglycerides 0.5% Perfume 0.2% Phase B Water ad 100.0% Phase C Sodium cocoamphoacetate 5.6% Phase D Lauryl glucoside 4.4% Phase E Coco-glucoside 1.2% Phase F Sodium / disodium cocoyl glutamate 3.6% Water 10.0% glycerin 0.7% Phase G Water 10.0% Xanthan gum 2.0% Phase H Citric Acid ad pH 6.0 Phase I Preservative qs Tab. 18: Shampoo Phase A Product Example C 2.0% Caprylic / Capric Triglycerides 0.5% Perfume 0.2% Phase B Water ad 100.0% Phase C Sodium Lauryl Sulfate 9.0% Phase D Cocamidopropyl betaines 3.0% Phase E Cocamide MEA 1.9% Xanthan gum 0.2% Water 10.0% Phase F Water 10.0% Polyquaternium-10 0.2% Phase G Citric Acid ad pH 5.7 Phase H Preservative qs Tab. 19: Deodorant Phase A Product Example E 3.0% Glycine Soybean (Soybean) Oil 0.2% Perfume 0.1% Phase B phenoxyethanol 0.5% Caprylyl glycol 0.2% Phase C Water 50.0% Hydroxethyl cellulose 0.75% Sodium hydroxides (10% in water) 0.25% Phase D Aluminum Chlorohydrate 19.0% Phase E Water ad 100.0% Tab. 20: Cleansing Oil Shampoo Water ad 100.0% Sodium Laureth Sulfate 7.0% MIPA-Laureth Sulfate 4.0% Sodium Chloride 3.2% Cocamidopropyl betaines 3.0% Product Example E 3.0% glycerin 2.5% PEG-18 Castor Oil Dioleate 2.0% Propylene glycol; PEG-55 Propylene Glycol Oleate 2.0% Laureth-5 Carboxylic Acid 1.0% Persea Gratissima (avocado) Oil 1.0% Polyglyceryl-6-caprylates; Polyglyceryl-4 caprate; Propylene glycol 0.9% Sodium benzoate 0.7% Salicylic Acid 0.3% linalool 0.2% alpha-isomethyl-ionone 0.1% Limonene 0.1% Zea Mays (Corn) Germ oil 0.2% Argania Spinosa Oil 0.1% Camellia Oleifera Seed Oil 0.1% Sodium hydroxides 0.3% Citric Acid ad pH 5.0 Perfume, Dyes qs Tab. 21: Pampering Oil Bath Water ad 100% Glycine Soy Oil 20.0% Product Example B 10.0% Polyglyceryl-3 palmitates 4.5% Glyceryl caprylates 4.5% Simmondsia Chinensis Seed Oil 1.5% Prunus Amygdalus Dulcis (Sweet Almond) Oil 1.0% Triticum Vulgare Germ Oil 1.0% tocopherol 0.2% Limonene 0.1% linalool 0.1% Citral 0.1% Dyes qs Tab. 22: Shower Cream Water ad 100% glycerin 7.5% Glycine Soy Oil 3.0% Lauryl glucoside 3.0% Sodium Coco Sulfate 3.0% Product Example C 2.5% Alcohol 1.5% Xanthan gum 1.5% Butyrospermum Parkii Butter Extract 1.2% Sodium Cetearyl Sulfate 1.0% Sodium Cocoyl Glutamate 1.0% Disodium Cocoyl Glutamate 1.0% tocopherol 0.1% Helianthus Annuus Seed Oil 0.3% Limonene 0.1% Benzyl Salicylate 0.1% linalool 0.1% Dyes qs Tab. 23: Shower gel Water ad 100% Sodium Coco Sulfate 5.0% glycerin 5.0% Lauryl glucoside 4.0% Sodium lactate 2.5% Product Example D 2.0% Polyglyceryl-4 Caprate 2.0% Sodium Cocoyl Glutamate 2.0% Disodium Cocoyl Glutamate 2.0% Alcohol 1.0% Prunus Cerasus Fruit Extract 1.0% Polyglyceryl-6-caprylates; Polyglyceryl-4 caprate; Propylene glycol 1.0% Limonene 0.1% coumarin 0.2% linalool 0.1% Citral 0.1% Dyes qs Tab. 24: Liquid Soap Water ad 100% glycerin 7.0% Alcohol 4.0% Sodium Coco Sulfate 3.0% Lauryl glucoside 2.5% Product Example E 2.0% Xanthan gum 1.5% Mangifera Indica (Mango) Fruit Extract 0.7% Limonene 0.1% linalool 0.1% Dyes qs Tab. 25: Shampoo for Children Water ad 100% Sodium Coco Sulfate 7.0% Decyl glucosides 5.0% Lactis proteinum 3.5% Sorbitan caprylates 3.0% Product Example F 3.0% glycerin 2.5% Sodium lactate 2.5% Alcohol 2.0% Hydrolyzed Wheat Protein 0.7% Hydrolyzed Wheat Starch 0.7% Sodium Chloride 0.9% Limonene 0.1% Citral 0.1% Phenethyl alcohol 0.1% Dyes qs Tab. 26: Cream Soap Water ad 100% Alcohol 5.0% Coco-glucoside 5.0% glycerin 5.0% Product Example F 2.5% Disodium Cocoyl Glutamate 2.0% Xanthan gum 1.5% Citric Acid ad pH 5.5 Malva Sylvestris Leaf Extract 1.0% Glyceryl Oleate 1.0% Sodium Cocoyl Glutamate 0.7% linalool 0.1% Limonene 0.1% Dyes qs Tab. 27: Make-up Remover Sodium cocoamphopropionate 5.0% Propylene glycol 35.0% Product Example F 30.0% glycerin 30.0% Preservative qs Tab. 28: Make-up Remover Cocamidopropyl betaines 8.0% Water 79.0% Product Example E 3.0% glycerin 10.0% Citric Acid ad pH 5.5 Preservative qs Tab. 29: Solution for wet wipes Product Example E 1.5% Perfume 0.2% glycerin 2.0% Sodium lactate; Sodium PCA; Glycine; fructose; Urea; Niacinamide; inositol; Sodium benzoate; Lactic acid 0.2% Water 95.6% Preservative qs Tab. 30: Solution for wet wipes Product Example E 2.0% Isopropyl myristate 0.3% phenoxyethanol; methyl paraben; Ethylparaben; Butylparaben; propyl paraben; Isobutylparaben 0.2% Perfume 0.1% Propylene glycol 3.0% Water 94.0% Cetrimonium bromides 0.1% Tab. 31: O / W make-up remover wipe Phase A Ethylhexyl stearate; phenoxyethanol; Polyglyceryl-4 laurate; Sorbitan laurate; Dilauryl citrate 4.0% Cetyl ricinoleates 0.8% Phase B Water ad 100.0% glycerin 1.5% Phase C Product Example C 1.0% Phase D phenoxyethanol 0.1% Perfume qs Preservative qs Tab. 32: Micellar water Water ad 100.0% Product Example D 5.0% glycerin 1.5% Disodium Cocoamphodiacetate 0.5% Disodium EDTA 0.2% Polyaminopropyl biguanides 0.2% Citric Acid, 30% ad pH 5.5 Table 33: Micellar Solution Cleanser Water ad 100.0% Butylene glycol 5.0% Coco-glucoside 2.0% Product Example D 2.0% glycerin 1.0% allantoin 0.1% Cistus Incanus Extract; maltodextrin 0.2% Perfume 0.2% Citric Acid, 30% ad pH 5.5 Table 34: Cleansing Water Water ad 100.0% Product Example E 2.5% phenoxyethanol; Ethylhexylglycerin 0.9% Caprylic / Capric Triglycerides 0.5% glycerin 0.5% Disodium EDTA 0.2% Citric Acid, 30% ad pH 5.5 Tab. 35: Cream shower Water ad 100% Ammonium Lauryl Sulfate 10.0% Product Example D 2.0% Aloe Barbadensis Leaf Juice 2.0% Cocamidopropyl betaines 2.0% Decyl glucosides 1.0% glycerin 1.0% Prunus Amygdalus Dulcis Oil 0.5% Glyceryl Oleate 0.3% Lauryl glucoside 0.3% Coco-glucoside 0.4% Benzyl Alcohol 0.2% Benzoic Acid 0.3% Dehydroacetic acid 0.2% Sodium benzoate 0.3% Potassium sorbates 0.2% tocopherol 0.1% Citric Acid ad pH 4.5 Perfume, Dyes qs Tab. 36: Cream shower Water ad 100% Sodium Laureth Sulfate 8.0% Product Example F 3.0% Cocamidopropyl betaines 3.0% glycerin 1.0% glucose 0.5% Prunus Amygdalus Dulcis Oil 0.7% Sodium Chloride 0.3% Polyquaternium-7 0.3% Styrene / acrylate copolymer 0.4% PEG-200 Hydrogenated Glyceryl Palmate; PEG-7 glyceryl cocoate 0.5% Citric Acid ad pH 5.5 Perfume, Dyes qs Tab. 37: Nursing shower Water ad 100% Sodium Laureth Sulfate 9.0% Sodium Hydroxypropyl Starch Phosphate 2.5% Product Example E 2.0% Cocamidopropyl betaines 2.0% petrolatum 1.0% Sodium Cocoyl Glycinate 1.0% Lauric Acid 0.5% Sodium lauroyl isethionate 0.5% glycerin 0.4% Helianthus Annuus Seed Oil 0.3% Olea Europaea Fruit Oil 0.2% Sodium Chloride 0.4% Stearic acid 0.5% Guar hydroxypropyltrimonium chlorides 0.2% Sodium isethionate 0.1% Tetrasodium EDTA 0.1% Alumina 0.1% Citric Acid ad pH 5.5 Perfumes, Dyes, Preservatives qs Tab. 38: Cream shower Water ad 100% Sodium coco sulphate 15.0% glycerin 3.5% Product Example F 3.5% Glycine Soy Oil 0.5% Coco-glucoside 0.8% Caprylic / Capric Triglycerides 0.2% Xanthan gum 0.8% Prunus Amygdalus Dulcis Oil 0.1% Simmondsia Chinensis Seed Oil 0.1% Sodium Cocoyl Glutamate 0.3% Disodium Cocoyl Glutamate 0.5% Sodium Cetearyl Sulfate 0.2% tocopherol 0.1% Helianthus Annuus Seed Oil 0.1% Alcohol 0.5% Citral 0.1% geraniol 0.1% Limonene 0.1% linalool 0.1% Citric Acid ad pH 5.8 Perfume, Dyes qs Tab. 39: Further formulation examples 39a 39b 39c 39d 39e 39f 39g 39h 39i 39j water ad 100% Product Example D 3.0% 4.0% 5.5% 1.0% 3.0% 3.0% 5.0% 4.0% 3.5% 3.0% Sodium Laureth Sulfate 9.0% 8.0% 9.0% - - - - - - - Sodium Lauryl Sulfate - - - 6.0% - - - - 3.5% - Cocamidopropyl betaines - 2.0% 3.0% 7.0% 5.0% 6.0% - - 2.0% 7.0% Sodium cocoamphoacetate 3.0% - - 1.5% 4.5% - 3.0% - 3.5% - Lauryl glucoside - - - - 3.5% 5.0% 3.0% 7.0% - - Coco-glucoside - 2.0% - - 1.5% 1.0% 5.5% 2.5% 2.0% - Sodium Cocoyl Glutamate - - - - - 1.0% 1.7% 5.0% 0.5% - Stearic acid - - 1.0% - - - - - 0.1% 3.5% Glyceryl glucosides - 0.3% - - 0.3% - 0.2% - - - Sucrose cocoate 0.5% - 1.0% 1.0% 0.3% 0.2% - 1.0% 1.0% 1.0% glycerin 0.5% 1.0% 0.5% - 0.3% 0.4% 1.5% 1.0% 0.5% 1.0% PEG-7 glyceryl cocoate - 0.3% - - - - - - - 0.5% Trideceth-9 - 0.2% - - 0.2% - - - - - Polysorbate 20 - -0.5% - - - - - - 0.3% 0.2% PEG-40 Hydrogenated Castor Oil - - 0.3% - 0.5% - - - 1.0% - PEG-6 Caprylic / Capric Glycerides - - - - 0.3% - - - 0.2% 0.2% Polyglyceryl-4 Caprate - - - 2.0% - 0.5% - 0.5% - 0.5% Polyquaternium-10 - 0.2% - 0.1% - - - 0.2% 0.2% - Hydroxypropyl Guar Hydroxypropyltrimonium Chloride 0.2% - 0.3% 0.2% 0.2% 0.2% 0.2% 0.1% - - Silicone Quaternium-22 - - 0.3% - 0.3% - - - - - Dimethicone - 0.3% - - - - - - 0.1% - amodimethicone - 0.1% - 0.1% 0.1% - - - 0.5% - Argania Spinosa Oil - - 0.2% 0.1% 0.1% - 0.2% - - - Prunus Amygdalus Dulcis Oil 0.2% - 0.2% 0.3% - 0.1% - - 0.2% 0.2% Olea Europaea Fruit Oil 0.2% 0.1% - - - 0.1% - 0.2% 0.1% - Butyrospermum Parkii Butter Extract - - 0.2% - 0.1% - - - - - Persea Gratissima Oil - - - 0.1% - 0.1% 0.2% - - - Hydrogenated Castor Oil - 0.2% - 0.1% - - - - 0.1% 0.2% Glycol distearate - 0.5% - - 0.5% - 0.3% - 0.5% 0.5% Isostearamide MIPA; Glyceryl laurate 1.0% - - 1.5% - - 0.2% - 1.0% 0.5% Cocamide DEA - - 0.5% - - 1.0% - - - - Sodium Chloride 0.3% 1.2% 1.0% 0.5% - 1.0% - 1.0% - 0.3% PEG-120 methyl glucose dioleate 0.2% 3.5% 1.0% - 1.5% - - - 0.5% - Xanthan gum - - 0.5% 0.8% - 0.7% 2.0% 1.0% - - cellulose - - - 0.1% - 0.1% 0.1% 0.2% 0.1% - Zinc Pyrithione - 0.1% - - - - - - 0.1% - Benzophenone-4 - 0.1% 0.1% 0.1% 0.1% - 0.1% - 0.1% - Tetrasodium EDTA 0.1% 0.1% - 0.1% 0.1% - - - 0.1% - Caffeine - 0.1% 0.1% - - - - 0.1% 0.1% - Hydrolyzed keratin - - 0.1% - - 0.1% 0.2% 0.1% 0.1% - panthenol 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% - 0.1% 0.1% 0.1% Citric Acid ad pH 5.5 Perfumes, Dyes, Preservatives qs Table 40: Further Formulation Examples 40a 40b 40c 40d 40e 40f 40g 40h 40i 40j water ad 100% Product Example F 9.0% 5.0% 5.0% 4.0% 4.0% 2.5% 6.0% 4.0% 3.0% 3.0% Sodium Lauryl Sulfate - 8.0% 8.0% - - - - 3.5% - - Coco-Betaine - 5.0% - 5.5% - - - 3.0% - - Cocamidopropyl betaines - -3.0% 3.0% -5.0% 5.0% - - - 3.0% 2.0% Sodium cocoamphoacetate - - 2.5% 3.0% - 5.0% - 3.0% 4.0% - Disodium Lauryl Sulfosuccinate - - 1.0% - - - - 1.2% - - Coco-glucoside - - - 3.0% 5.0% 4.0% 5.0% 1.0% - 2.0% Sodium Cocoyl Glutamate - - - 2.5% - 3.0% 4.5% 0.5% 2.5% 0.3% Stearic acid - - 0.3% - - - - 0.1% - 0.5% Sodium Cocoyl Glycinate - - - - 5.0% -3.5% 3.5% - 2.0% 7.0% Sodium Lauroyl Methyl Isethionate - 1.0% - 1.5% - 1.0% 0.5% 0.5% Sucrose cocoate 0.5% 0.4% - 1.0% - - 0.2% 0.3% 1.0% 0.3% glycerin 1.5% 0.3% 0.5% 0.5% 0.3% 0.5% 1.0% 0.5% 0.3% 1.0% PEG-40 Hydrogenated Castor Oil - 1.0% - - - - - 0.3% - - Polyglyceryl-4 Caprate 0.5% - - 0.5% - 2.6% - - 1.1% - Polyquaternium-11 - 0.2% - - 0.1% - - 0.2% - 0.3% Guar hydroxypropyltrimonium chlorides - - 0.3% 0.2% 0.2% 0.3% 0.2% 0.1% 0.2% - Dimethicone - 0.3% - - - - - 0.2% - - Aminopropyl dimethicone - 0.3% 0.5% - - - - 0.3% - - Helianthus Annuus Seed Oil 0.3% - 0.1% 0.5% - 0.1% 0.1% 0.2% - 0.1% Olea Europaea Fruit Oil 0.2% 0.1% 0.2% - 0.2% 0.1% 0.2% - 0.6% 0.2% PEG-3 distearate - 0.5% - - - - - 0.5% - - Acrylates / C10-30 Alkyl Acrylate Crosspolymer 0.5% - 0.4% - 0.5% 0.4% - - 0.5% - Sodium hydroxides, 25% 0.6% - 0.6% - 0.8% 0.5% - - 0.7% - Cocamide MEA - 0.8% 1.0% 1.0% - 0.2% 0.6% 1.0% - 0.3% Sodium Chloride 0.2% 0.7% 0.2% - 0.2% 0.1% - 1.0% 0.2% 1.0% Propylene glycol; PEG-55 Propylene Glycol Oleate - 2.5% - - - - - 0.8% - - Xanthan gum 0.2% - 0.2% 1.5% 0.5% - 1.8% 0.2% 1.1% 0.9% Hydroxyethyl ethyl cellulose 0.1% - - 0.1% - 0.1% 0.1% - - - Benzophenone-4 - 0.1% 0.2% - - - - 0.2% - 0.1% menthol 0.1% - 0.1% - - 0.1% - 0.1% 0.1% 0.1% Caffeine - - 0.1% - 0.1% - - 0.1% - 0.1% Benzyl Alcohol 0.1% - - - - 0.1% - 0.1% - - coumarin 0.1% - 0.1% 0.1% - - 0.1% 0.1% - 0.1% Hydrolyzed Wheat Protein - - 0.1% 0.1% 0.1% 0.2% 0.2% 0.1% - - panthenol 0.1% 0.1% - 0.1% 0.1% 0.1% 0.1% - 0.1% 0.1% Citric Acid ad pH 5.2 Perfumes, Dyes, Preservatives qs Table 41: Further Formulation Examples 41a 41b 41c 41d 41e 41f 41g 41h 41i 41j water ad 100% Product Example E 3.5% 3.0% 2.5% 4.0% 3.0% 4.0% 6.0% 4.0% 5.0% 4.0% MIPA-Laureth Sulfate 10.5% 5.0% - - - - - - - - Sodium C14-16 olefin sulfonates - - 8.0% - - - - - 3.5% - Coco-Betaine - 4.0% - 5.5% - - 4.0% 3.5% - Cocamidopropyl betaines 2.0% - 4.0% - 5.0% 5.0% - - - 4.0% Sodium cocoamphopropionate - - 1.0% - 2.0% - 1.5% 4.0% 2.0% 3.5% Coco-glucoside - 2.5% - 2.5% 3.0% - 4.5% 3.5% 2.0% 0.5% Sodium Cocoyl Glutamate - - - 1.5% 1.0% 1.5% 1.5% 1.5% 0.8% 0.3% Lauric Acid - 0.5% - - - 1.0% - 2.0% - 4.5% Sodium Cocoyl Glycinate - - - 2.5% - 5.0% - - 0.8% 0.5% Sodium cocoyl sarcosinate - 0.7% 0.5% - - 1.0% 0.5% - - - dicaprylyl 0.5% - - - - 0.2% - - - - glycerin 0.5% 0.3% 0.5% 1.5% 0.4% 0.5% 1.0% 0.5% 0.3% 1.0% Polysorbate 20 0.5% - - - - 0.5% - - - 0.4% Polyglyceryl-4 Laurate 0.5% - 0.4% 0.3% - - 0.5% - 1.1% - Polyquaternium-37 0.4% - - 0.1% - - - 0.2% 0.1% - Hydroxypropyl Guar Hydroxypropyltrimonium Chloride - 0.2% 0.1% 0.2% - - 0.3% - 0.2% - Cassia Hydroxypropyltrimonium Chloride - 0.1% - - 0.2% - - - - - Sodium Hydroxypropyl Starch Phosphate 0.2% - - - - 0.4% - - - 0.5% Hydroxypropyl methyl cellulose 0.2% - - 0.2% 0.2% - - - 0.2% - Dimethicone 0.2% - - - - 1.0% - - 0.3% - Aminopropyl dimethicone 0.2% 0.4% - - - 0.5% - - - 0.5% Palmitamidopropyltrimonium Chloride 0.3% - 0.5% - - - - - 0.4% - Persea Gratissima (avocado) Oil 0.1% 1.1% - 0.1% 0.2% - 0.3% - 0.1% 0.1% Butyrospermum Parkii Butter Extract 0.2% - 0.1% - - 0.3% - - - - Prunus Amygdalus Dulcis Oil 0.2% - 0.2% 0.2% - - 0.2% 0.5% - - Glycol distearate 0.5% 0.7% - - 0.5% 0.8% - - 0.4% 0.3% Carbomer - 0.3% - - - 0.5% 0.7% - 0.5% - Sodium hydroxides, 25% - 0.5% - - - 0.7% 1.0% - 0.8% - Isostearamide MIPA; Glyceryl laurate 0.7% - 0.8% - 0.3% 0.3% - 0.4% - 0.3% Sorbitan sesquicaprylates - - 0.2% 1.0% - - 0.4% 1.0% - 0.7% Sodium Chloride 0.8% - 0.3% 0.2% 0.5% - - 2.0% - - PEG-18 Glyceryl Oleate / Cocoate 0.8% - - - - 0.6% - - - 0.9% Xanthan gum - 1.0% 0.2% 1.0% - 0.2% 0.3% - - 0.2% algin - 0.2% - - 1.0% - - - 1.2% - Caragenaan 0.5% - - 0.3% - - - 0.3% - 0.2% silica 0.1% - 0.1% - - 0.2% - - 0.2% 0.1% Cetearyl Alcohol 0.2% - - - 0.3% 0.2% - - - 0.3% Benzophenone-4 0.1% 0.1% 0.2% - 0.2% 0.2% - - - 0.1% Tetrasodium EDTA 0.1% 0.1% - 0.1% 0.1% 0.2% 0.1% - 0.2% 0.1% Octopirox® 0.2% - - - - 0.1% - - - - Zinc PCA - - 0.1% - - - - - - 0.1% Creatine 0.1% - 0.1% 0.1% - 0.1% 0.1% 0.1% - 0.1% Hydrolyzed collagen - - - 0.1% - 0.1% - 0.1% 0.1% 0.1% Salicylic Acid 0.1% - - - 0.1% 0.1% - - 0.1% 0.1% panthenol 0.1% 0.1% - 0.1% 0.1% 0.1% 0.1% - 0.1% 0.1% Lactic acid 0.2% - 0.2% - 0.1% 0.5% 0.3% - 0.2% - PEG-14M 0.3% - - - - 0.4% - - - 0.3% 1,2-Hexanediol 0.3% - - - - 0.3% - 0.2% - - Citric Acid ad pH 5.5 Perfumes, Dyes, Preservatives qs <b> Table 42: List of raw materials used </ b> INCI Trade name, company 1,2-Hexanediol Hydrolite-6 841129, Symrise Acrylates / beheneth-25 methacrylate copolymer Novethix L-10 polymer, Lubrizole Acrylates / C10-30 Alkyl Acrylate Crosspolymer TEGO Carbomer 841 SER, Evonik Industries AG, 100% algin Hydagen 558P, BASF allantoin Allantoin, DSM Nutritional Products, Inc. Aloe Barbadensis Leaf Juice Aloe-Con UP 40, Florida Food Products Inc. alpha-isomethyl-ionone alpha-isomethylionone, Chemos GmbH Alumina Aeroxide Alu C, Evonik Industries AG Aluminum Chlorohydrate Locron L, Clariant Ammonium Lauryl Sulfate Empicol AL 70, Albright & Wilson UK Limited Aminopropyl dimethicone ABIL Soft AF 200, Evonik Industries AG amodimethicone DC 949, Dow Corning, 100% Argania Spinosa Oil (Argania Spinosa Kernel Oil) Argan Oil, DSM Nutritional Products Ltd. Benzophenone-4 Uvinul MS 40, BASF Corporation Benzoic Acid OriStar BZA, Orient Stars LLC Benzyl Alcohol Microcare BNA, THOR PERSONAL CARE SAS Benzyl Salicylate Seridefrizz Intense, Cheemyunion Quimica Ltda. Butylene glycol Butylene Glycol, Oxea Corporation Butyrospermum Parkii Butter Extract Cosmosil 600, International Cosmetic Science Center Caffeine Caffeine, Merck KGaA / EMD Chemicals, Inc. Camellia Oleifera Seed Oil Camellia Sasanqua Oil, Ikeda Corporation Caprylyl glycol Sensiva SC 10, Schülke & Mayr GmbH Caprylic / Capramidopropyl Betaine TEGO Betaine 810, Evonik Industries AG, 38% Caprylic / Capric Triglycerides TEGOSOFT CT, Evonik Industries AG, 100% carrageenan All Carrageenan, CP Kelco Carbomer TEGO Carbomer 140, Evonik Industries AG, 100% Cassia Hydroxypropyltrimonium Chloride Form start Sensomer ST 250-Polymer, Lubrizol end of form cellulose Arbocel A300, J. Rettenmaier & Sons Cetearyl Alcohol TEGO Alkanol 1618, Evonik Industries AG, 100% Cetyl ricinoleates TEGOSOFT CR, Evonik Industries AG, 100% Cetrimonium bromides Rhodaquat M-242B / 99, Rhodia Chamomilla Recutita (Matricaria) Extract Recentia CR, Akzo Nobel Global Personal Care Citral Citral FF, Symrise AG Citric Acid Citric Acid USP Granular, DSM Nutritional Products, Inc. Citrus Aurantifolia (Lime) Oil AEC Lime Oil, A & E Connock, Perfumery & Cosmetics Ltd. Cistus Incanus Extract; maltodextrin TEGO Cistus, Evonik Industries AG Cocamide DEA REWOMID DC 212 S, Evonik Industries AG, 100% Cocamide MEA REWOMID D 212, Evonik Industries AG, 100% Cocamidopropyl betaines TEGO Betain F 50, Evonik Industries AG, 38% Coco-glucoside Plantacare 818 UP, BASF Cognis, 51% Coco-Betaine Dehyton AB 30, BASF Cognis, 31% coumarin Rhodiascent extra pure, Rhodia Organics Creatine TEGO Cosmo C 100, Evonik Industries AG, 100% Decyl glucosides Plantacare 2000 UP, BASF Cognis dicaprylyl Cetiol OE, BASF Cognis Dehydroacetic acid Unisept DHA (Universal Preserv-A-Chem, Inc.) Dimethicone DC 200 Fluid 100 cSt, Dow Corning, 100% Disodium Cocoamphodiacetate Rewoteric AM 2 C NM, Evonik Industries AG Disodium Cocoyl Glutamate Planatpon ACG LC, BASF Cognis Disodium EDTA Dissolvine NA-2-P, Akzo Nobel Global Personal Care Disodium Lauryl Sulfosuccinate REWOPOL SB F 12P, Evonik Industries AG, 95% Ethylhexyl stearate; phenoxyethanol; Polyglyceryl-4 laurate; Sorbitan laurate; Dilauryl citrate TEGO Wipe Flex, Evonik Industries AG geraniol Nerol 800, International Flavors & Fragrances Inc. glucose Organic Biovert Substrate, Lonza glycerin Glycerol EP, vegetable, Spiga North, 99.7% Glyceryl caprylates Dermosoft GMCY, dr. Straetmans Glyceryl glucosides Hydagen GG, BASF Cognis Glyceryl Oleate TEGIN OV, Evonik Industries AG Glycine Soybean (Soybean) Oil Cropure Soybean, Croda Europe, Ltd. Glycol distearate TEGIN G 1100, Evonik Industries AG, 100% Guar hydroxypropyltrimonium chlorides Cosmedia Guar C 261, BASF Personal Care and Nutrition Gmbh / Jaguar C-17, Rhodia Inc. and others Helianthus Annuus (Sunflower) Seed Oil AEC Sunflower Oil, A & E Connock, Perfumery & Cosmetics Ltd. Hydrogenated Castor Oil Cutina HR Powder, BASF Personal Care and Nutrition Gmbh Hydrolyzed collagen Nutrilan H, BASF Personal Care and Nutrition Gmbh Hydrolyzed keratin Kerasol, Croda, Inc. Hydrolyzed Wheat Protein Gluadin WLM, BASF Cognis Hydrolyzed Wheat Starch Cropeptide W, Croda, Inc. Hydroxyethyl ethyl cellulose Structure Cel 4400 E, Akzo Nobel Global Personal Care Hydroxypropyl Guar Hydroxypropyltrimonium Chloride Jaguar C-162, Rhodia, 100% Hydroxypropyl methyl cellulose TEGOCEL HPM 50, Evonik Industries AG, 100% Isopropyl myristate TEGOSOFT M, Evonik Industries AG, 100% Isostearamide MIPA; Glyceryl laurate ANTIL SPA 80, Evonik Industries AG, 100% Lactic acid AEC Lactic Acid, A & E Connock, Perfumery & Cosmetics Ltd. Lactis proteinum AEC Whey Protein, A & E Connock, Perfumery & Cosmetics Ltd. Laureth-4 TEGO Alkanol L 4, Evonik Industries AG, 100% Laureth-5 Carboxylic Acid Marlowet 1072, Sasol Germany GmbH - Marl Lauric Acid Prifrac 2920, Croda Europe, Ltd. Lauryl glucoside Plantacare 1200 UP, BASF Cognis, 50% lecithin AEC Lecithin Powder, A & E Connock, Perfumery & Cosmetics Ltd. Limonene Dipentene No. 122, Hercules Inc. linalool Lipofresh, Lipo Chemicals, Inc. Magnesium chlorides OriStar MCL, Orient Stars LLC maltodextrin Farmal MD 10, Corn Products International Malva Sylvestris (Mallow) Leaf Extract Herbasec Mallow Leaves, Cosmetochem International AG Mangifera Indica (Mango) Fruit Extract Mango Extract, Draco Natural Products menthol OriStar MC, Orient Stars LLC MIPA-Laureth Sulfate Zetesol 2056, Zschimmer & Schwarz GmbH Octopirox® Octopirox, Clariant Intl. Ltd. Olea Europaea (Olive) Fruit Oil Cropure Olive, Croda Europe, Ltd. Palmitamidopropyltrimonium Chloride VARISOFT PATC, Evonik Industries AG, 60% panthenol D-panthenol USP, BASF, 100% PEG-120 methyl glucose dioleate ANTIL 120 Plus, Evonik Industries AG, 100% PEG-14M Polyox WSR-205, The Dow Chemical Company PEG-18 Castor Oil Dioleate Marlowet CG, Sasol Germany GmbH PEG-18 Glyceryl Oleate / Cocoate ANTIL 171, Evonik Industries AG, 100% PEG-200 Hydrogenated Glyceryl Palmate; PEG-7 glyceryl cocoate REWODERM LI S 80, Evonik Industries AG, 100% PEG-3 distearate TEGIN D 1102, Evonik Industries AG, 100%; Cutina TS, BASF Cognis, 100% PEG-40 Hydrogenated Castor Oil TAGAT CH 40, Evonik Industries AG, 100% PEG-40 Sorbitan Peroleates Arlatone T, Croda PEG-6 Caprylic / Capric Glycerides TEGOSOFT GMC-6, Evonik Industries AG, 100% PEG-7 glyceryl cocoate TEGOSOFT GC, Evonik Industries AG, 100% Persea Gratissima (avocado) Oil Cropure avocado, Croda Europe, Ltd. petrolatum Merkur 115, Sasol Wax GmbH Phenethyl alcohol Etaphen, Vevy Europe SpA phenoxyethanol S & M Phenoxyethanol, Schülke & Mayr GmbH phenoxyethanol; Ethylhexyl glycerin Euxyl PE 9010, Schülke & Mayr GmbH phenoxyethanol; methyl paraben; Ethylparaben; Butylparaben; propyl paraben; Isobutylparaben Euxyl K 300, Schuelke & Mayr GmbH Polyaminopropyl biguanides Microcare MBG, Thor Polyglyceryl-3 palmitates Dermofeel PP, dr. Straetmans Polyglyceryl-4 Caprate TEGOSOFT PC 41, Evonik Industries AG, 100% Polyglyceryl-6-caprylates; Polyglyceryl-4 caprate; Propylene glycol TEGO Solve 55, Evonik Industries AG, Polyquaternium-10 Polymer JR 400, Amerchol, 100% Polyquaternium-11 Dehyquart CC 11, BASF Personal Care and Nutrition Gmbh / Luviquat PQ 11 PN, BASF Corporation Polyquaternium-37 Cosmedia Ultragel 300, BASF Personal Care and Nutrition Gmbh Polyquaternium-7 Merquat 550, Nalco, 100% Polysorbate 20 TEGO SML 20, Evonik Industries AG, 100% Potassium sorbates Euxyl K 712, Schülke & Mayr GmbH Propylene glycol Euxyl K 320, Schülke & Mayr GmbH Propylene glycol; PEG-55 Propylene Glycol Oleate ANTIL 141 Liquid, Evonik Industries AG Prunus Amygdalus Dulcis (Sweet Almond) Oil Cropure Almond, Croda Europe, Ltd. Prunus Cerasus (Bitter Cherry) Fruit Extract Prunus Cerasus Fruit, cherries Extract, Botanica GmbH Ricinus Communis Seed Oil Lipovol CO, Lipo Chemicals Salicylic Acid OriStar SCA, Orient Stars LLC silica Aerosil 130, Evonik Degussa GmbH Silicone Quaternium-22 ABIL T quat 60, Evonik Industries AG, 65% Silicone Quaternium-22; Polyglycerol-3 caprate; Dipropylene glycol; Cocamidopropyl betaines ABIL ME 45, Evonik Industries AG, 30% Simmondsia chinensis (Jojoba) Seed Oil AEC Jojoba Oil Refined, A & E Connock, Perfumery & Cosmetics Ltd. Sodium benzoate Euxyl K 712, Schülke & Mayr GmbH Sodium C14-16 olefin sulfonates Bioterge AS-40 AOS, Stepan, Sodium Cetearyl Sulfate Lanette E, BASF Personal Care and Nutrition Gmbh Sodium cocoamphoacetate REWOTERIC AM C, Evonik Industries AG, 32% Sodium cocoamphopropionate REWOTERIC AT KSF 40, Evonik Industries AG, 40% Sodium coco sulphate Texapon HC G, BASF Sodium Cocoyl Glutamate Plantapon ACG HC, BASF Cognis Sodium Cocoyl Glycinate Hostapon SG, Clariant; Amilite GCS-11, Ajinomoto Sodium cocoyl sarcosinate Crodasinic CS, Croda Sodium / disodium cocoyl glutamate PERLASTAN SC 25 trucks, Schill & Seilacher, 25%, Sodium hydroxides Unichem SOHYD, Universal Preserv-A-Chem, Inc. Sodium Hydroxypropyl Starch Phosphate Pure-Gel, Grain Processing Corporation Sodium isethionate Hostapon SI, Company Clariant International Ltd, Sodium lactate Sodium Lactate Solution About 50%, Merck KGaA / EMD Chemicals, Inc. Sodium lactate; Sodium PCA; Glycine; fructose; Urea; Niacinamide; inositol; Sodium benzoate; Lactic acid LACTIL, Evonik Industries AG Sodium Laureth Sulfate Texapon NSO, BASF Cognis, 28% Sodium lauroamphoacetate ColaTeric SLAA, Colonial Chemical Inc Sodium lauroyl isethionate Yongan SLI, Huanggang Yongan Pharmaceutical Co., Ltd Sodium Lauroyl Methyl Isethionate Iselux, Innospec Active Chemicals Sodium Lauryl Sulfate Texapon LS 35, BASF Cognis, 30% Sodium Trideceth Sulfate Rhodapex EST-30, Rhodia Sorbitan caprylates Sorbon S-10, Toho Chemical Industry Co., Ltd. Sorbitan sesquicaprylates ANTIL Soft SC, Evonik Industries AG, 100% Stearic acid Pristerene 4922, Croda Europe, Ltd. Styrene / acrylate copolymer Acudyne HS, The Dow Chemical Company Sucrose cocoate TEGOSOFT LSE 65K, Evonik Industries AG, 100% Tetrasodium EDTA Versene 100, The Dow Chemical Company tocopherol Euxyl K 700, Schülke & Mayr GmbH Trideceth-9 Marlipal O 13/90, Sasol Germany GmbH - Marl Triticum Vulgare Germ Oil Cropure Wheatgerm, Croda Europe, Ltd. Xanthan gum Keltrol CG-SFT, CP Kelco, 100% Zea Mays (Corn) Germ oil AEC Corn Germ Oil, A & E Connock, Perfumery & Cosmetics Ltd. Zinc PCA Zincidone, UCIB, Solabia Group Zinc Pyrithione Microcare ZP, THOR PERSONAL CARE SAS

Claims (17)

1. Polyglycerol partial ester of the general formula I

   

   where

   n = 2 to 16, preferably 4 to 14, particularly preferably 5 to 11,

   R¹, R², R³ = independently of one another, identical or different, selected from H, R⁴ and R⁵, where

   R⁴ =saturated or unsaturated acyl residue having 6 - 22 carbon atoms, preferably 8 - 18 carbon atoms, comprising no hydroxyl groups,

   R⁵ =saturated or unsaturated acyl residue having 6 - 22 carbon atoms, preferably 14 - 22 carbon atoms, comprising at least one hydroxyl group or an acyl residue of an oligomer of saturated or unsaturated acyl residues having 6 - 22 carbon atoms, preferably 14 - 22 carbon atoms, comprising at least one hydroxyl group,

   characterized in that the molar ratio of the acyl residues R⁴ to R⁵ is in a range of 95:5 to 5:95.
2. Polyglycerol partial ester according to Claim 1, characterized in that R⁴ and R⁵ are acyl residues of fatty acids.
3. Polyglycerol partial ester according to Claim 1 or 2, characterized in that at least 50 mol% of the R⁴ acyl residues are selected from capryloyl, caproyl and lauroyl residues, based on all R⁴ residues in the polyglycerol partial ester.
4. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that R⁵ is selected from ricinoyl and hydroxystearoyl residues, their oligomers and mixtures thereof.
5. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that at least 90 mol% of the R⁵ acyl residues comprise ricinoyl residues or a mixture of ricinoyl and hydroxystearoyl residues, based on all R⁵ residues in the polyglycerol partial ester.
6. Polyglycerol partial ester according to at least one of Claims 1 to 4, characterized in that R⁵ is selected from ricinoyl residues.
7. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that the weight ratio of the polyglyceryl residue to the sum total of the acyl residues R⁴ and R⁵ is 85:15 to 55:45.
8. Method for preparing polyglycerol partial esters according to Claim 1 comprising the method steps of:

   A) providing a polyglycerol having a mean degree of polymerisation n = 2 to 16,

   B) acylation of some of the hydroxyl groups of the polyglycerol with
   at least one first carboxylic acid derivative of one or more first, saturated or unsaturated carboxylic acids having 6 - 22 carbon atoms comprising no hydroxyl groups and
   at least one second carboxylic acid derivative of one or more second, saturated or unsaturated carboxylic acids having 6 - 22 carbon atoms comprising at least one hydroxyl group or an oligomer of the second carboxylic acid,
   in which the carboxylic acid derivatives are selected from carboxylic acids and carboxylic esters,

   wherein the molar ratio of the acyl residues of the first carboxylic acid derivative used in method step B) to those of the second carboxylic acid derivative is in a range of 95:5 to 5:95.
9. Method according to Claim 8 or 9, characterized in that in method step B)
   at least one first carboxylic acid and at least one second carboxylic acid,
   at least one first carboxylic ester and at least one second carboxylic acid,
   at least one first carboxylic acid and at least one second carboxylic ester,
   at least one first carboxylic ester and at least one second carboxylic ester,
   at least one first carboxylic acid and at least one first carboxylic ester and at least one second carboxylic acid,
   at least one first carboxylic acid and at least one first carboxylic ester and at least one second carboxylic ester,
   at least one first carboxylic acid and at least one second carboxylic acid and at least one second carboxylic ester,
   at least one first carboxylic ester and at least one second carboxylic acid and at least one second carboxylic ester,
   or
   at least one first carboxylic acid and at least one first carboxylic ester and at least one second carboxylic acid and at least one second carboxylic ester,
   are used.
10. Method according to Claim 8 or 9, characterized in that at least 50 mol% of the first carboxylic acids are selected from caprylic acid, capric acid and lauric acid, based on the acyl residues of all the first carboxylic acid derivatives.
11. Method according to at least one of Claims 8 to 10, characterized in that at least 90 mol% of the second carboxylic acids are selected from ricinoleic acid and hydroxystearic acid, based on the acyl residues of all the second carboxylic acid derivatives.
12. Method according to at least one of Claims 8 to 11, characterized in that at least 90 mol% of the second carboxylic acids comprise ricinoleic acid and hydroxystearic acid, and the second carboxylic acids have a molar ratio of ricinoleic acid residues to hydroxystearic acid residues in a range of 100 to 0.1 to 50 to 50, based on the acyl residues of all the second carboxylic acid derivatives.
13. Method according to at least one of Claims 8 to 12, characterized in that the weight ratio of the polyglycerol to the sum total of the acyl residues of the first and second carboxylic acid derivatives used is 85:15 to 55:45.
14. Method according to at least one of Claims 8 to 13, characterized in that the molar ratio of the acyl residues of saturated to unsaturated carboxylic acid derivatives used in method step B) is 99:1 - 1:99.
15. Formulation comprising at least one polyglycerol partial ester according to at least one of Claims 1 to 7.
16. Formulation according to Claim 15, comprising

    0.1% by weight to 40% by weight of polyglycerol partial ester according to at least one of Claims 1 to 7

    0.01% by weight to 40% by weight of oil-soluble substance and

    10% by weight to 98% by weight of water.
17. Use of at least one polyglycerol partial ester according to at least one of Claims 1 to 7 for solubilizing at least one oil-soluble substance in water.